CN103880020B - Chirality mesoporous organic silica nanotube or core-shell type nanometer rod and preparation method thereof - Google Patents
Chirality mesoporous organic silica nanotube or core-shell type nanometer rod and preparation method thereof Download PDFInfo
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Abstract
Chirality mesoporous organic silica nanotube or core-shell type nanometer rod and preparation method thereof, belong to chirality mesoporous technical field of nano material.The present invention uses hard template method first, transmitted by chirality, prepare high-quality chirality mesoporous organic silica nanotube or core-shell type nanometer rod, its size is controlled very all in the lump, this method is simply efficient, and the chirality mesoporous organic silica nanotube prepared shows high-specific surface area (500 ~ 1200m
2g
-1) and high pore volume (0.6 ~ 1.0cm
3g
-1), tube wall be rich in homogeneous mesoporous passage and point to central shaft, and function organic group is evenly distributed in mesoporous wall, these characteristics make chirality mesoporous organic silica nanotube of the present invention or core-shell type nanometer rod will in catalysis, and drug loading and the field such as chiral recognition and chiral separation have wide practical use.
Description
Technical field
The invention belongs to chirality mesoporous technical field of nano material, be specifically related to one with chirality mesoporous silicon dioxide nano rod for hard template, under the guidance of organosilane, by the method for one step growth induced corrosion, obtain chirality mesoporous organic silica nanotube or core-shell type nanometer rod.
Background technology
Chirality characteristic is extensively present in the compound of large nature, particularly common in organic compound, nearest chirality mesoporous silica nano material is in the news as a kind of inorganic materials with chirality characteristic, due to its high-specific surface area, aperture is adjustable, pattern is various and the chirality of its adjustable change and by extensive concern, have special using value in chiral catalysis, chiral recognition and chiral separation etc.
Meanwhile, chirality mesoporous Silica Nanotube, because its density is lower and utilizable larger cavity, makes it have larger application prospect.The people such as ShunaiChe (Chem.Mater.2007,19,1577-1583) in acid condition, with achiral surfactant sodium dodecyl base sodium sulfonate for template, with N-trimethoxy silicon propyl group-N, N, N-trimethyl ammonium chloride is respectively co-structured directed agents and chiral doping body with (R)-(+)-2-amino-3-phenyl-1-propanol or (S)-(-)-2-amino-3-phenyl-1-propanol, has synthesized the chirality mesoporous Silica Nanotube that pattern is comparatively regular.The people such as YonggangYang (Chem.Commun., 2008,4948 – 4950) in neutral conditions, adopt the low-molecular-weight parents' polymkeric substance of chirality to be template, be co-structured directed agents with aminopropyl trimethoxysilane, synthesize the chiral hybrid Silica Nanotube of pattern comparatively rule.
Above synthetic method belongs to soft template method, needs to use special chirality to be situated between and sees template or chiral doping body, do not have duct or duct to be parallel to central shaft above the tube wall of chiral hybrid Silica Nanotube.
Summary of the invention
The object of this invention is to provide a kind of simply effective and controlled hard template method, transmitted by chirality, prepare mesoporous organic silica nanotube or core-shell type nanometer rod and preparation method thereof that high quality has chirality.
The present invention is under the guidance of organosilane, and by the method for one step growth induced corrosion, obtain mesoporous organic silica nanotube or the core-shell type nanometer rod with chirality, this method is adapted to different organosilanes and structural parameter height is controlled.
The invention provides a kind of chirality mesoporous organic silica nanotube or core-shell type nanometer rod, it is characterized in that, described mesoporous organic silica is a kind of pattern rule, the chiral nanotubes shape structure of size uniformity or chirality core-shell type nano bar-shape structure, the diameter (external diameter of particle) of mesoporous organic silica nanotube is 100 ~ 200nm, length is 400 ~ 800nm, and thickness of pipe is 10 ~ 30nm, mesoporous organic silica core-shell type nanorod structure is for core with the chirality mesoporous silicon dioxide nano rod of rich less mesoporous (aperture is about 2.3 ~ 2.8nm) and unordered more mesoporous (aperture is about 15 ~ 30nm) in order, with mesoporous organic silica for shell, the diameter of core is 50 ~ 150nm, length is 400 ~ 800nm, the thickness of shell is 10 ~ 30nm, rich very homogeneous mesoporous on the tube wall of nanotube and the shell of chirality core-shell type nanometer rod, its aperture is 2.5 ~ 4.0nm, and point to central shaft, function organic group (comprises methylene radical, vinyl, vinylidene and phenylene etc.) homogeneous be distributed in mesoporous hole wall, its specific surface area is 500 ~ 1200m
2g
-1, pore volume is 0.6 ~ 1.0cm
3g
-1.
The preparation method of chirality mesoporous organic silica nanotube of the present invention, comprises the following steps:
(1) adopt sol-gel method, seeing template with the non-chiral surface's promoting agent mixed for being situated between, obtaining the chirality mesoporous silicon dioxide nano rod reaction solution that size is controlled;
Described non-chiral surface's promoting agent is the mixing of a kind of nonionic surface active agent and a kind of cationic surfactant, both mass ratioes are 1.4 ~ 2.5:1, wherein nonionic surface active agent is triblock copolymer P123, F127(PEOPPOPEO) etc., cationic surfactant is cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, octadecyl trimethyl ammonium chloride etc.;
Described sol-gel method, non-chiral surface's promoting agent of mixing is at room temperature dissolved in water and ammoniacal liquor that volume ratio is 29:1 ~ 29:3, then the tetraethoxy that volume is ammoniacal liquor 0.5 ~ 0.9 times is added, 2 ~ 6h is reacted under room temperature, chirality mesoporous silicon dioxide nano rod reaction solution can be obtained, nanorod length is 600 ~ 800nm, width is 50 ~ 150nm, its length and width can be adjusted by the add-on of tetraethoxy, the mol ratio of mixing non-chiral surface's promoting agent and water is 1:150 ~ 1:200, described ammoniacal liquor is strong aqua, its mass concentration is 25 ~ 28%,
(2) add organosilane in the reaction solution obtained to step (1), under room temperature, react 2 ~ 6h, after organosilane complete hydrolysis, load in high pressure stainless steel cauldron, then under 80 ~ 100 degree aging 1 ~ 24h;
Described organosilane is bridging type organosilane, and its structural formula is as follows:
(R
1O)
3-Si-R-Si-(OR
1)
3
Wherein R
1for CH
3or C
2h
5; R is organic functions group, comprises methylene radical (-CH
2-), vinyl (-CH
2cH
2-), vinylidene (-CH=CH-) and phenylene (-Ph-) etc., what described bridging type organosilane was concrete can be two (triethoxysilyl) methane, 1, two (triethoxysilyl) ethane, 1 of 2-, 2-two (triethoxysilyl) ethene, Isosorbide-5-Nitrae-bis-(triethoxysilyl) benzene etc.;
The volume of added organosilane is 0.1 ~ 0.6 times of ammoniacal liquor, its detailed process is: with the chirality mesoporous silicon dioxide nano rod of gained in step (1) for hard template, under the guidance of organosilane, by one step growth induced corrosion, namely while tube wall growth, chirality mesoporous silicon dioxide nano rod is corroded gradually, and be hydrolyzed by the silicate ion that dissolves and organosilane together with the oligopolymer obtained and the tube wall that copolycondensation forms nanotube occurs, last chirality mesoporous silicon dioxide nano rod is dissolved completely, obtain chirality mesoporous organic silica nanotube, if digestion time is foreshortened to 1 ~ 4h, or regulate and control kind and the consumption of organosilane, chirality mesoporous silicon dioxide nano rod is by the dissolving of part, namely chirality mesoporous organic silica core-shell type nanometer rod is obtained (with the rich orderly less mesoporous and unordered silicon-dioxide chirality nanometer rod more mesoporous be partly solubilized for core, with mesoporous organic silica for shell), and its chirality is by transmitting to be got off by complete maintenance.
(3) product of step (2) is obtained chirality mesoporous organic silica nanotube or core-shell type nanometer rod successively after centrifugal, washing, drying, extraction removing tensio-active agent.
The last handling process that step (3) is product.Wherein washing refers to wash 1 ~ 5 time respectively with water and ethanol, the dry drying conditions that can adopt routine, as dried 3 ~ 24h under 50 ~ 100 degree, described extraction removing tensio-active agent can by product backflow 3 ~ 24h in acid ethanol solution (volume ratio of concentrated hydrochloric acid and ethanol is 0.1:100 ~ 2:100, and the massfraction of concentrated hydrochloric acid is 36%); Centrifugal condition is 8000 ~ 15000 revs/min, and centrifugation time is 5 ~ 10 minutes.
The present invention uses hard template method first, transmitted by chirality, prepare high-quality chirality mesoporous organic silica nanotube or core-shell type nanometer rod, its size is controlled very all in the lump, this method is simply efficient, and the chirality mesoporous organic silica nanotube prepared shows high-specific surface area (500 ~ 1200m
2g
-1) and high pore volume (0.6 ~ 1.0cm
3g
-1), tube wall be rich in homogeneous mesoporous passage and point to central shaft, and function organic group is evenly distributed in mesoporous wall, these characteristics make chirality mesoporous organic silica nanotube of the present invention or core-shell type nanometer rod will in catalysis, and drug loading and the field such as chiral recognition and chiral separation have wide practical use.
Accompanying drawing explanation
Fig. 1: the stereoscan photograph of chirality mesoporous organic (ethane) Silica Nanotube that embodiment 1 obtains.
Fig. 2: the low power (left figure) of chirality mesoporous organic (ethane) Silica Nanotube that embodiment 1 obtains and high power (right figure) transmission electron microscope photo.
Fig. 3: the little angle XRD spectra of chirality mesoporous organic (ethane) Silica Nanotube that embodiment 1 obtains.
Fig. 4: the N of chirality mesoporous organic (ethane) Silica Nanotube that embodiment 1 obtains
2adsorption-desorption isothermal and pore size distribution curve thereof.
Fig. 5: the stereoscan photograph of chirality mesoporous organic (benzene) Silica Nanotube that embodiment 2 obtains.
Fig. 6: the low power (left figure) of chirality mesoporous organic (benzene) Silica Nanotube that embodiment 2 obtains and high power (right figure) transmission electron microscope photo.
Fig. 7: the little angle XRD spectra of chirality mesoporous organic (benzene) Silica Nanotube that embodiment 2 obtains.
Fig. 8: the N of chirality mesoporous organic (benzene) Silica Nanotube that embodiment 2 obtains
2adsorption-desorption isothermal and pore size distribution curve thereof.
Embodiment
Set forth the present invention further below in conjunction with specific embodiment, should be understood that these embodiments are only not used in for illustration of the present invention and limit the scope of the invention.
Embodiment 1
After 29mL water and 1mL ammoniacal liquor (mass concentration is 25%) are mixed, add F127 and cetyl trimethylammonium bromide 0.123g and 0.3g respectively, after room temperature lower magnetic force is stirred to dissolving, add tetraethoxy 0.6mL fast, magnetic agitation 2h, add organosilane 1 again, two (triethoxysilyl) ethane 0.3mL of 2-, magnetic agitation 2h, after complete hydrolysis, load in high pressure stainless steel cauldron, aging 24h under 100 degree.After being cooled to room temperature, centrifugation, wash twice respectively with water and ethanol, 80 degree of dry 10h, carry out extraction with 50mL acid ethanol solution (volume ratio of concentrated hydrochloric acid and ethanol is 1:70) and remove tensio-active agent, obtain chirality mesoporous organic (ethane) Silica Nanotube, quality is about 0.14g.
The scanning electron microscope (SEM) photograph of chirality mesoporous organic (ethane) Silica Nanotube obtained in this example as shown in Figure 1, by clearly finding out in figure that particle is very homogeneous chirality nano bar-shape pattern, length is 700 ~ 800nm, and diameter is 120 ~ 160nm, and its transmission electron microscope picture as shown in Figure 2, the nano tubular structure of chirality can be confirmed as further, nanometer rod is around central shaft distortion, and some places are compact, as white arrow, some places loosen, as black arrow.And on tube wall, rich sensing central shaft is mesoporous, and thickness of pipe is 16nm, its little angle XRD spectra and N
2respectively as shown in Figure 3 and Figure 4, illustrate that the mesoporous distribution on tube wall is narrow, aperture is 3.2nm to adsorption-desorption curve, and specific surface area is 512m
2g
-1, pore volume is 0.67cm
3g
-1.Embodiment 2
After 29mL water and 1mL ammoniacal liquor (mass concentration is 25%) are mixed, add F127 and cetyl trimethylammonium bromide 0.123g and 0.3g respectively, after room temperature lower magnetic force is stirred to dissolving, add tetraethoxy 0.6mL fast, magnetic agitation 2h, add organosilane 1 again, two (triethoxysilyl) benzene 0.3mL of 4-, magnetic agitation 2h, after complete hydrolysis, load in high pressure stainless steel cauldron, aging 24h under 100 degree.After being cooled to room temperature, centrifugation, wash twice respectively with water and ethanol, 80 degree dry 10 hours, carry out extraction with 50mL acid ethanol solution (volume ratio of concentrated hydrochloric acid and ethanol is 1:70) and remove tensio-active agent, obtain chirality mesoporous organic (benzene) silica core-core-shell type nanometer rod, quality is about 0.19g.
The scanning electron microscope (SEM) photograph of chirality mesoporous organic (benzene) silica core-core-shell type nanometer rod obtained in this example as shown in Figure 5, by clearly finding out in figure that particle is very homogeneous chirality nano bar-shape pattern, length is 700 ~ 800nm, diameter is 120 ~ 160nm, its transmission electron microscope picture as shown in Figure 6, the core-shell type nano bar-shape structure of chirality can be confirmed as further, core is the chirality mesoporous silicon dioxide nano rod of rich less mesoporous (aperture is 2.5nm) and unordered more mesoporous (aperture is 18nm) in order, shell is mesoporous organic (benzene) silicon-dioxide, thickness is 16nm, its mesopore orbit points to central shaft, the diameter of core is 100 ~ 150nm, length is 700 ~ 800nm, its little angle XRD spectra as shown in Figure 7, orderly mesoscopic structure illustrates that the chirality mesoporous silicon dioxide nano rod of hard template is only by slight corrosion, its N2 adsorption-desorption curve and pore size distribution curve are as shown in Figure 8, further illustrate chirality mesoporous silicon dioxide nano rod only by slight corrosion, formed and be about the unordered more mesoporous of 18nm, simultaneously in order less mesoporously still exist, aperture is 2.5nm, the mesoporous pore size of mesoporous organic (benzene) silica shell is 2.8nm, its specific surface area is 1097.3m
2g
-1, pore volume is 1.13cm
3g
-1.
Embodiment 3
After 29mL water and 1mL ammoniacal liquor (mass concentration is 25%) are mixed, add F127 and cetyl trimethylammonium bromide 0.123g and 0.3g respectively, after room temperature lower magnetic force is stirred to dissolving, add tetraethoxy 0.6mL fast, magnetic agitation 2h, add organosilane 1 again, two (triethoxysilyl) ethane 0.4mL of 2-, magnetic agitation 2h, after complete hydrolysis, load in high pressure stainless steel cauldron, aging 24h under 100 degree.After being cooled to room temperature, centrifugation, wash twice respectively with water and ethanol, 80 degree of dry 10h, carry out extraction with 50mL acid ethanol solution (volume ratio of concentrated hydrochloric acid and ethanol is 1:70) and remove tensio-active agent, obtain chirality mesoporous organic (ethane) Silica Nanotube that tube wall is thicker, quality is about 0.16g.If within digestion time is foreshortened to 4h, obtain the product of nucleocapsid structure.
Chirality mesoporous organic (ethane) Silica Nanotube obtained in this example, its thickness of pipe is about 25nm, and length is 700 ~ 800nm, and diameter is 120 ~ 160nm.
Embodiment 4
After 29mL water and 1.5mL ammoniacal liquor (mass concentration is 25%) are mixed, add F127 and cetyl trimethylammonium bromide 0.123g and 0.183g respectively, after room temperature lower magnetic force is stirred to dissolving, add tetraethoxy 0.6mL fast, magnetic agitation 2h, add organosilane 1 again, two (triethoxysilyl) ethane 0.3mL of 2-, magnetic agitation 2h, after complete hydrolysis, load in high pressure stainless steel cauldron, aging 24h under 100 degree.After being cooled to room temperature, centrifugation, wash twice respectively with water and ethanol, 80 degree of dry 10h, carry out extraction with 50mL acid ethanol solution (volume ratio of concentrated hydrochloric acid and ethanol is 1:70) and remove tensio-active agent, obtain different size, chirality mesoporous organic (ethane) Silica Nanotube that tube wall is thinner, quality is about 0.08g.If within digestion time is foreshortened to 4h, obtain the product of nucleocapsid structure.
Chirality mesoporous organic (ethane) Silica Nanotube obtained in this example, its thickness of pipe is about 10nm, and diameter is 110 ~ 150nm, and length is 400 ~ 500nm.
Embodiment 5
After 29mL water and 1mL ammoniacal liquor (mass concentration is 25%) are mixed, add F127 and Cetyltrimethylammonium bromide 0.123g and 0.3g respectively, after room temperature lower magnetic force is stirred to dissolving, add tetraethoxy 0.6mL fast, magnetic agitation 2h, add organosilane 1 again, two (triethoxysilyl) ethane 0.3mL of 2-, magnetic agitation 2h, after complete hydrolysis, load in high pressure stainless steel cauldron, aging 24h under 100 degree.After being cooled to room temperature, centrifugation, wash twice respectively with water and ethanol, 80 degree of dry 10h, carry out extraction with 50mL acid ethanol solution (volume ratio of concentrated hydrochloric acid and ethanol is 1:70) and remove tensio-active agent, obtain mesoporous larger chirality mesoporous organic (ethane) Silica Nanotube, quality is about 0.14g.If within digestion time is foreshortened to 4h, obtain the product of nucleocapsid structure.
Chirality mesoporous organic (ethane) Silica Nanotube obtained in this example, its thickness of pipe is about 16nm, and diameter is 120 ~ 160nm, and length is 700 ~ 800nm, and aperture is about 3.6nm, and specific surface area is 578m
2g
-1, pore volume is 0.78cm
3g
-1.
The specific surface area of chirality mesoporous organic silica nanotube prepared by above-described embodiment and comparative example, pore volume and pore size distribution are respectively according to Brunauer – Emmett – Teller(BET) and Barrett-Joyner-Halenda(BJH) method calculating.
Claims (6)
1. a chirality mesoporous organic silica nanotube, is characterized in that: the external diameter of mesoporous organic silica nanotube is 100 ~ 200nm, and length is 400 ~ 800nm, and thickness of pipe is 10 ~ 30nm; The tube wall of nanotube is rich in mesoporous, its aperture is 2.5 ~ 4.0nm, and points to central shaft, and methylene radical, vinyl, vinylidene or phenylene function organic group are distributed in mesoporous hole wall, and its specific surface area is 500 ~ 1200m
2/ g, pore volume is 0.6 ~ 1.0cm
3/ g.
2. the preparation method of chirality mesoporous organic silica nanotube according to claim 1, its step is as follows:
(1) adopt sol-gel method, seeing template with the non-chiral surface's promoting agent mixed for being situated between, obtaining the chirality mesoporous silicon dioxide nano rod reaction solution that size is controlled; Non-chiral surface's promoting agent is the mixing of a kind of nonionic surface active agent and a kind of cationic surfactant, both mass ratioes are 1.4 ~ 2.5:1, wherein nonionic surface active agent is triblock copolymer P123 or F127, and cationic surfactant is cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Cetyltrimethylammonium bromide or octadecyl trimethyl ammonium chloride;
(2) organosilane 1 is added in the reaction solution obtained to step (1), two (triethoxysilyl) ethane of 2-, the volume of organosilane is 0.1 ~ 0.6 times of ammoniacal liquor, 2 ~ 6h is reacted under room temperature, after organosilane complete hydrolysis, load in high pressure stainless steel cauldron, then under 80 ~ 100 degree aging 24h;
(3) product of step (2) is obtained chirality mesoporous organic silica nanotube successively after centrifugal, washing, drying, extraction removing tensio-active agent.
3. the preparation method of chirality mesoporous organic silica nanotube as claimed in claim 2, it is characterized in that: sol-gel method is at room temperature dissolved in by non-chiral surface's promoting agent of mixing in water and ammoniacal liquor that volume ratio is 29:1 ~ 29:3, then the tetraethoxy that volume is ammoniacal liquor 0.5 ~ 0.9 times is added, 2 ~ 6h is reacted under room temperature, chirality mesoporous silicon dioxide nano rod reaction solution can be obtained, nanorod length is 600 ~ 800nm, and width is 50 ~ 150nm; The mol ratio of mixing non-chiral surface's promoting agent and water is 1:150 ~ 1:200; Described ammoniacal liquor is strong aqua, and its mass concentration is 25 ~ 28%; Washing refers to wash 1 ~ 5 time respectively with water and ethanol, and drying dries 3 ~ 24h under 50 ~ 100 degree, and extraction is the 3 ~ 24h that refluxed in acid ethanol solution by product; Centrifugal condition is 8000 ~ 15000 revs/min, and centrifugation time is 5 ~ 10 minutes.
4. a chirality mesoporous organic silica core-shell type nanometer rod, it is characterized in that: mesoporous organic silica core-shell type nanometer rod is that to be rich in aperture be that less mesoporous and aperture is the unordered chirality mesoporous silicon dioxide nano rod more mesoporous of 15 ~ 30nm to 2.3 ~ 2.8nm is in order core, with mesoporous organic silica for shell, the diameter of core is 50 ~ 150nm, length is 400 ~ 800nm, and the thickness of shell is 10 ~ 30nm; The shell of core-shell type nanometer rod is rich in mesoporous, its aperture is 2.5 ~ 4.0nm, and points to central shaft, and methylene radical, vinyl, vinylidene or phenylene function organic group are distributed in mesoporous hole wall, and its specific surface area is 500 ~ 1200m
2/ g, pore volume is 0.6 ~ 1.0cm
3/ g.
5. the preparation method of chirality mesoporous organic silica core-shell type nanometer rod according to claim 4, its step is as follows:
(1) adopt sol-gel method, seeing template with the non-chiral surface's promoting agent mixed for being situated between, obtaining the chirality mesoporous silicon dioxide nano rod reaction solution that size is controlled; Non-chiral surface's promoting agent is the mixing of a kind of nonionic surface active agent and a kind of cationic surfactant, both mass ratioes are 1.4 ~ 2.5:1, wherein nonionic surface active agent is triblock copolymer P123 or F127, and cationic surfactant is cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Cetyltrimethylammonium bromide or octadecyl trimethyl ammonium chloride;
(2) organosilane 1 is added in the reaction solution obtained to step (1), two (triethoxysilyl) ethane of 2-, the volume of organosilane is 0.1 ~ 0.6 times of ammoniacal liquor, 2 ~ 6h is reacted under room temperature, after organosilane complete hydrolysis, load in high pressure stainless steel cauldron, then under 80 ~ 100 degree aging 1 ~ 4h; Or add organosilane 1 in the reaction solution to obtain to step (1), two (triethoxysilyl) benzene of 4-, the volume of organosilane is 0.1 ~ 0.6 times of ammoniacal liquor, 2 ~ 6h is reacted under room temperature, after organosilane complete hydrolysis, load in high pressure stainless steel cauldron, then under 80 ~ 100 degree aging 24h;
(3) product of step (2) is obtained chirality mesoporous organic silica core-shell type nanometer rod successively after centrifugal, washing, drying, extraction removing tensio-active agent.
6. the preparation method of chirality mesoporous organic silica core-shell type nanometer rod as claimed in claim 5, it is characterized in that: sol-gel method is at room temperature dissolved in by non-chiral surface's promoting agent of mixing in water and ammoniacal liquor that volume ratio is 29:1 ~ 29:3, then the tetraethoxy that volume is ammoniacal liquor 0.5 ~ 0.9 times is added, 2 ~ 6h is reacted under room temperature, chirality mesoporous silicon dioxide nano rod reaction solution can be obtained, nanorod length is 600 ~ 800nm, and width is 50 ~ 150nm; The mol ratio of mixing non-chiral surface's promoting agent and water is 1:150 ~ 1:200; Described ammoniacal liquor is strong aqua, and its mass concentration is 25 ~ 28%; Washing refers to wash 1 ~ 5 time respectively with water and ethanol, and drying dries 3 ~ 24h under 50 ~ 100 degree, and extraction is the 3 ~ 24h that refluxed in acid ethanol solution by product; Centrifugal condition is 8000 ~ 15000 revs/min, and centrifugation time is 5 ~ 10 minutes.
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| Synthesis of pH-responsive mesoporous silica nanotubes for controlled release;Jie Ma et al.;《J Sol-Gel Sci Technol》;20131220;第69卷(第2期);第364-369页 * |
| Template-Directed Synthesis of Silica Nanowires and Nanotubes from Cylindrical Core-Shell Polymer Brushes;Markus Mullner et al.;《Chemistry of Materials》;20120425;第24卷(第10期);第1802-1810页 * |
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